CN114957981A - Lubricating wear-resistant enhanced engineering plastic alloy and preparation method thereof - Google Patents
Lubricating wear-resistant enhanced engineering plastic alloy and preparation method thereof Download PDFInfo
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- CN114957981A CN114957981A CN202210690467.8A CN202210690467A CN114957981A CN 114957981 A CN114957981 A CN 114957981A CN 202210690467 A CN202210690467 A CN 202210690467A CN 114957981 A CN114957981 A CN 114957981A
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 46
- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 35
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 5
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 5
- 239000012745 toughening agent Substances 0.000 claims abstract description 5
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 4
- 239000000945 filler Substances 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims abstract description 3
- 239000002135 nanosheet Substances 0.000 claims description 65
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 43
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000005461 lubrication Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 6
- 229960001231 choline Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229940119177 germanium dioxide Drugs 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 229960000281 trometamol Drugs 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 abstract description 10
- 229920002647 polyamide Polymers 0.000 abstract description 10
- 239000004677 Nylon Substances 0.000 abstract description 4
- 229920001778 nylon Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Abstract
The invention discloses a lubricating wear-resistant reinforced engineering plastic alloy and a preparation method thereof, belonging to the field of modified engineering plastics and comprising the following components in parts by weight: 100 parts of PA6 polyamide resin, 2-5 parts of polyether ether ketone resin, 1-4 parts of polytetrafluoroethylene resin, 2-10 parts of toughening agent, 10-15 parts of reinforcing agent, 10-18 parts of wear-resisting agent, 3-8 parts of lubricant, 0-6 parts of pigment and filler and 0.01-0.1 part of stabilizer; the invention modifies the polyamide nylon resin by adjusting and matching the components, improves the comprehensive mechanical property and the friction property, can be widely used as products requiring good self-lubricating property and wear resistance, and enlarges the application range and the use value of the polyamide nylon resin in the field of engineering plastic alloys.
Description
Technical Field
The invention relates to the field of modified engineering plastics, in particular to a lubricating wear-resistant reinforced engineering plastic alloy and a preparation method thereof.
Background
The engineering plastic can be used as engineering material and replace metal to manufacture machine parts and other plastics, has excellent comprehensive performance, high rigidity, small creep, high mechanical strength, high heat resistance, high electric insulation, can be used in harsh chemical and physical environments for a long time, can replace metal to be used as engineering structural material, but has higher price and lower yield, compared with general plastic, the engineering plastic can reach higher requirements in the aspects of mechanical property, durability, corrosion resistance, heat resistance and the like, is more convenient to process and can replace metal material, the engineering plastic is widely applied to industries such as electronics, automobiles, buildings, office equipment, machinery, aerospace and the like, the steel is replaced by the plastic, the wood is replaced by the plastic, the engineering plastic has become the international popular trend, the engineering plastic has become the field with the fastest growth speed in the plastic industry of the world, the development of the engineering plastic not only plays a supporting role for the national pillar industry and the modern high and new technology industry, meanwhile, the improvement of the traditional industry and the adjustment of the product structure are promoted, and the application of the engineering plastics to automobiles is increasing, and the engineering plastics are mainly used as bumpers, fuel tanks, instrument panels, body panels, automobile doors, automobile lamp covers, fuel pipes, radiators, relevant parts of engines and the like.
The reinforced polyamide composite material has the characteristics of high physical and mechanical properties, good thermal stability, good electrical properties, corrosion resistance and the like, is widely applied to industries such as automobiles, electronics and electrical, national defense and military industry, mechanical equipment and the like, the application field of the polyamide composite material is continuously expanded, higher requirements are provided for the properties such as toughness, strength and the like of the polyamide material, compared with other engineering plastics, the polyamide material is usually used in the manufacturing fields such as gears, bearings and the like, but the polyamide has high friction coefficient and poor wear resistance under dry conditions, and the wide application of the polyamide composite material in the engineering mechanical field is limited.
Disclosure of Invention
Aiming at the problems, the invention provides a lubricating wear-resistant reinforced engineering plastic alloy and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
the lubricating wear-resistant reinforced engineering plastic alloy comprises the following components in parts by weight:
100 parts of PA6 polyamide resin, 2-5 parts of polyether ether ketone resin, 1-4 parts of polytetrafluoroethylene resin, 2-10 parts of toughening agent, 10-15 parts of reinforcing agent, 10-18 parts of wear-resisting agent, 3-8 parts of lubricant, 0-6 parts of pigment and filler and 0.01-0.1 part of stabilizer.
Preferably, the toughening agent is one or more of butyl benzyl phthalate, di-sec-octyl phthalate or dicyclohexyl phthalate.
Preferably, the reinforcing agent is a hard microsphere comprising one or more of glass microspheres, epoxy resin microspheres and ultrafine ceramic microspheres.
Preferably, the wear-resisting agent is a mixture of zinc germanate nanoparticle-loaded carbon nitride nanosheets, zirconium phosphate nanosheets and graphene nanosheets.
Preferably, the preparation method of the zinc germanate nanoparticle-supported carbon nitride nanosheet, zirconium phosphate nanosheet and graphene nanosheet mixture comprises the following steps:
s1 preparation of nanosheet
Respectively weighing and mixing dicyandiamide and cyanuric acid, heating to 500-550 ℃ at the speed of 2-5 ℃/min under the air condition, carrying out heat preservation and heat treatment for 2-4h to obtain a heat treatment product, dispersing the heat treatment product in concentrated hydrochloric acid solution, stirring for reaction overnight, separating and washing a precipitate, and ultrasonically dispersing the precipitate in deionized water to obtain C 3 N 4 A nanosheet dispersion;
wherein the molar ratio of the dicyandiamide to the cyanuric acid is (2-3): 1;
s2 hard particle loading
Respectively weighing zirconium phosphate nanosheet and grapheneNanosheet being ultrasonically dispersed in the C 3 N 4 Obtaining a dispersion liquid with the dispersion concentration of 1-5mg/mL in the nanosheet dispersion liquid, adding zinc acetate and completely dissolving to obtain a solution A; respectively weighing sodium carbonate and germanium dioxide, mixing the sodium carbonate and the germanium dioxide according to an equimolar ratio, heating the mixture to 900-1000 ℃ at the speed of 2-5 ℃/min, carrying out heat preservation treatment for 6-12h to obtain a product A, and dissolving the product A in deionized water to prepare a solution B with the concentration of 4-8 mg/mL; slowly adding the solution B into the solution A under the condition of violent stirring, heating to boil, keeping the temperature, stirring and reacting for 2-3 hours, cooling after the reaction is finished, centrifugally separating and precipitating, washing with ethanol and deionized water in sequence, and drying to obtain the product;
wherein the zirconium phosphate nano-sheet, the graphene nano-sheet and the C 3 N 4 The mass ratio of the nano sheets is (1-3): (0.5-1) (0.5-1); the concentration of zinc acetate in the solution A is 0.08-0.1 mol/L; the mixing volume ratio of the solution A to the solution B is 1: 1.
preferably, the zirconium phosphate nanosheets are alpha-zirconium phosphate nanosheets, and the preparation method thereof comprises the following steps:
weighing alpha-zirconium phosphate and dispersing the alpha-zirconium phosphate in deionized water to obtain a solution C; respectively weighing tromethamine, choline and triethanolamine as stripping aids, dissolving in deionized water to obtain a solution D, slowly adding the solution D into the solution C at room temperature under stirring conditions, continuing stirring for reaction for 1-30min after the addition is finished, performing high-speed centrifugal separation and precipitation after ultrasonic dispersion, and drying to obtain the alpha-zirconium phosphate nanosheets;
wherein the dispersion ratio of the alpha-zirconium phosphate is 2-4g/100 mL; the concentration of the tromethamine, the choline and the triethanolamine in the solution D is respectively 0.01-0.1mol/L, 0.04-0.1mol/L and 0.01-0.05mol/L, and the mixing volume ratio of the solution C to the solution D is 1: 1.
preferably, the preparation method of the zirconium phosphate nanosheet comprises the following steps:
weighing phenylphosphonic acid and dissolving the phenylphosphonic acid in deionized water to prepare a solution E with the concentration of 0.6-1 mol/L; respectively weighing zirconium oxychloride and hydrofluoric acid, preparing solutions F with the concentrations of 0.15-0.25mol/L and 1-1.5mol/L respectively, adding the solution E into the solution F with the same volume under the stirring condition, sealing a reaction system, carrying out heat preservation reaction at 70-80 ℃ for 36-48h, carrying out centrifugal separation and precipitation after the reaction is finished, washing, and carrying out vacuum drying to remove the solvent, thus obtaining the zirconium phosphate nanosheet.
Preferably, the lubricant is one or more of calcium stearate, ethylene bis-stearamide and pentaerythritol tetrastearate alcohol.
Preferably, the stabilizer is an organic tin stabilizer or an organic antimony stabilizer.
The invention also aims to provide a preparation method of the lubricating wear-resistant reinforced engineering plastic alloy, which comprises the following steps:
(1) preparing the wear-resistant agent;
(2) preparing raw materials according to the proportion, firstly stirring and mixing the raw materials in a high-speed mixer for 1-30min, then feeding the dispersed raw materials into an extruder, heating the extruder at the temperature of 200-280 ℃ at the speed of 40-50rpm, and carrying out melt blending, extrusion, traction, cooling and grain cutting to obtain the lubricating wear-resistant reinforced engineering plastic alloy.
The invention has the beneficial effects that:
the invention provides a lubricating wear-resistant reinforced engineering plastic alloy, which modifies polyamide nylon resin through the adjustment and matching of components, improves the comprehensive mechanical property and the friction property, can be widely used as products requiring good self-lubricating property and wear resistance, and enlarges the application range and the use value of the polyamide nylon resin in the field of engineering plastic alloys; specifically, the polytetrafluoroethylene resin is introduced on the basis of the conventional lubricant, and the engineering plastic alloy is endowed with good self-lubricating property based on the lower surface property of the polytetrafluoroethylene resin; a small amount of polyether-ether-ketone resin is added into a resin matrix to reduce the influence of various introduced external doping aids on the strength of the alloy material and make up for the loss of strength; furthermore, according to the invention, a hard nanoparticle-loaded nanosheet material is added on the basis of the toughening and reinforcing assistant as an anti-wear agent, the wear resistance and lubricity of the engineering plastic alloy can be improved by the two-dimensional nanosheet material with good interlayer tribological performance, and meanwhile, the hard nanoparticles are introduced between the nanosheet layers, so that on one hand, the mechanical strength of the engineering plastic alloy can be ensured while the frictional performance is enhanced, and on the other hand, the hard nanoparticles are embedded between the nanosheet layers to separate the nanosheets, so that the wear resistance of the engineering plastic alloy is further promoted; in order to improve the dispersibility of the zirconium phosphate nanosheets in the resin matrix, the invention adds the stripping auxiliary agent on the basis of the existing ultrasonic stripping to enlarge the distance between the stripping layers, so that the zirconium phosphate nanosheets are more easily dispersed in the resin matrix, and the friction performance is further improved; in order to further overcome the polarity difference between the zirconium phosphate nanosheets and the resin matrix, phenyl phosphonic acid is used as a phosphorus source to introduce phenyl groups between the nanosheets, so that the interlayer spacing of the stripped layers is further enlarged, the affinity is improved, and the friction performance of the alloy material is further enhanced.
Detailed Description
The invention is further described in connection with the following examples.
Example 1
The lubricating wear-resistant reinforced engineering plastic alloy comprises the following components in parts by weight:
100 parts of PA6 polyamide resin, 3 parts of polyether-ether-ketone resin, 2 parts of polytetrafluoroethylene resin, 4 parts of dicyclohexyl phthalate, 12 parts of superfine ceramic microspheres, 10-18 parts of wear-resisting agent, 4 parts of calcium stearate and 0.05 part of organic tin stabilizer;
the preparation method comprises the following steps: preparing raw materials according to the proportion, stirring and mixing the raw materials in a high-speed mixer for 10min, feeding the dispersed raw materials into an extruder at the feeding speed of 40-50rpm, heating the extruder at 278 ℃, and performing melt blending, extrusion, traction, cooling and grain cutting to obtain the lubricating wear-resistant reinforced engineering plastic alloy;
the wear-resisting agent is a mixture of zinc germanate nanoparticle-loaded carbon nitride nanosheets, zirconium phosphate nanosheets and graphene nanosheets, and the preparation method comprises the following steps:
s1 preparation of nanosheet
Respectively weighing dicyandiamide and cyanuric acid, mixing, and stirring at 3 deg.C/min in airHeating to 550 ℃, carrying out heat preservation and heat treatment for 3 hours to obtain a heat treatment product, dispersing the heat treatment product in a concentrated hydrochloric acid solution, stirring for reaction overnight, separating and washing a precipitate, and then ultrasonically dispersing the precipitate in deionized water to obtain the compound C 3 N 4 A nanosheet dispersion;
wherein the molar ratio of the dicyandiamide to the cyanuric acid is 2.4: 1;
s2 hard particle loading
Respectively weighing zirconium phosphate nanosheets and graphene nanosheets, and ultrasonically dispersing in the C 3 N 4 Obtaining a dispersion liquid with the dispersion concentration of 3mg/mL in the nanosheet dispersion liquid, and adding zinc acetate to completely dissolve the zinc acetate to obtain a solution A; respectively weighing sodium carbonate and germanium dioxide, mixing the sodium carbonate and the germanium dioxide according to an equimolar ratio, heating the mixture to 900-1000 ℃ at the speed of 4 ℃/min, carrying out heat preservation treatment for 8 hours to obtain a product A, and dissolving the product A in deionized water to prepare a solution B with the concentration of 6.5 mg/mL; slowly adding the solution B into the solution A under the condition of violent stirring, heating to boil, keeping the temperature, stirring and reacting for 2 hours, cooling after the reaction is finished, centrifugally separating precipitate, washing with ethanol and deionized water in sequence, and drying to obtain the product;
wherein the zirconium phosphate nanosheets are prepared by ultrasonic dispersion of alpha-zirconium phosphate; the zirconium phosphate nanosheet, the graphene nanosheet and the C 3 N 4 The mass ratio of the nano sheets is 1.8: 0.7: 0.6; the concentration of zinc acetate in the solution A is 0.1 mol/L; the mixing volume ratio of the solution A to the solution B is 1: 1.
example 2
The lubricating and wear-resistant reinforced engineering plastic alloy is the same as that in example 1, except that the zirconium phosphate nanosheets are alpha-zirconium phosphate nanosheets, and the preparation method comprises the following steps:
weighing alpha-zirconium phosphate and dispersing the alpha-zirconium phosphate in deionized water to obtain a solution C; respectively weighing tromethamine, choline and triethanolamine as stripping aids, dissolving in deionized water to obtain a solution D, slowly adding the solution D into the solution C at room temperature under stirring conditions, continuing stirring for reaction for 10min after the addition is finished, performing high-speed centrifugal separation and precipitation after ultrasonic dispersion, and drying to obtain the alpha-zirconium phosphate nanosheets;
wherein the dispersion ratio of the alpha-zirconium phosphate is 3g/100 mL; the concentration of the tromethamine, the concentration of the choline and the concentration of the triethanolamine in the solution D are respectively 0.06mol/L, 0.08mol/L and 0.03mol/L, and the mixing volume ratio of the solution C to the solution D is 1: 1.
example 3
An engineering plastic alloy with enhanced lubrication and wear resistance is different from the engineering plastic alloy in example 1 in that the preparation method of the zirconium phosphate nanosheet comprises the following steps:
weighing phenylphosphonic acid and dissolving the phenylphosphonic acid in deionized water to prepare a solution E with the concentration of 0.8 mol/L; respectively weighing zirconium oxychloride and hydrofluoric acid, preparing solutions F with the concentrations of 0.2mol/L and 1.5mol/L respectively, adding the solution E into the solution F with the same volume under the stirring condition, sealing a reaction system, carrying out heat preservation reaction at 70-80 ℃ for 40h, carrying out centrifugal separation and precipitation after the reaction is finished, washing, and carrying out vacuum drying to remove the solvent, thus obtaining the zirconium phosphate nanosheet.
Example 4
An engineering plastic alloy with enhanced lubricating and wear resistance, which is the same as example 1, except that the anti-wear agent is not contained.
Example 5
An engineering plastic alloy with enhanced lubrication and wear resistance is the same as that in example 1, except that the wear-resistant agent is prepared from the following components in a mass ratio of 1.8: 0.7: 0.6 zirconium phosphate nanosheets, graphene nanosheets and said C 3 N 4 A mixture of nanoplates, the zirconium phosphate nanoplates made from alpha-zirconium phosphate ultrasound dispersion.
Example 6
An engineering plastic alloy with enhanced lubricating and wear resistance, which is the same as example 1, except that the polytetrafluoroethylene resin is not contained.
Examples of the experiments
The engineering plastic alloys prepared in examples 1 to 6 were tested for mechanical properties, wear resistance factor and friction properties, and the test results are shown in the following table:
| item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength/MPa | 82.1 | 83.2 | 84.5 | 70.6 | 76.3 | 75.8 |
| Flexural Strength/MPa | 100.2 | 103.8 | 109.4 | 92.7 | 96.6 | 94.5 |
| Taber abrasion/mg/1000 times | 3.2 | 2.5 | 2.3 | 5.4 | 4.8 | 3.6 |
| Coefficient of static friction/. mu.s | 0.33 | 0.32 | 0.33 | 0.38 | 0.47 | 0.62 |
| Coefficient of kinetic friction/. mu.k | 0.24 | 0.24 | 0.25 | 0.29 | 0.33 | 0.49 |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The lubricating wear-resistant reinforced engineering plastic alloy is characterized by comprising the following components in parts by weight:
100 parts of PA6 polyamide resin, 2-5 parts of polyether ether ketone resin, 1-4 parts of polytetrafluoroethylene resin, 2-10 parts of toughening agent, 10-15 parts of reinforcing agent, 10-18 parts of wear-resisting agent, 3-8 parts of lubricant, 0-6 parts of pigment and filler and 0.01-0.1 part of stabilizer.
2. The engineering plastic alloy with lubricating and wear-resisting enhancement function as claimed in claim 1, wherein the toughening agent is one or more of butyl benzyl phthalate, di-sec-octyl phthalate or dicyclohexyl phthalate.
3. The engineering plastic alloy with the lubricating and wear-resisting enhancement function as claimed in claim 1, wherein the reinforcing agent is hard microspheres comprising one or more of glass microspheres, epoxy resin microspheres and ultrafine ceramic microspheres.
4. The engineering plastic alloy with enhanced lubrication and wear resistance as claimed in claim 1, wherein the wear-resistant agent is a mixture of zinc germanate nanoparticle-supported carbon nitride nanosheets, zirconium phosphate nanosheets and graphene nanosheets.
5. The engineering plastic alloy with enhanced lubrication and wear resistance as claimed in claim 4, wherein the preparation method of the zinc germanate nanoparticle-supported carbon nitride nanosheet, zirconium phosphate nanosheet, graphene nanosheet mixture comprises the following steps:
s1 preparation of nanosheet
Respectively weighing and mixing dicyandiamide and cyanuric acid, heating to 500-550 ℃ at the speed of 2-5 ℃/min under the air condition, carrying out heat preservation and heat treatment for 2-4h to obtain a heat treatment product, dispersing the heat treatment product in concentrated hydrochloric acid solution, stirring for reaction overnight, separating and washing a precipitate, and ultrasonically dispersing the precipitate in deionized water to obtain C 3 N 4 A nanosheet dispersion;
wherein the molar ratio of the dicyandiamide to the cyanuric acid is (2-3): 1;
s2 hard particle loading
Respectively weighing zirconium phosphate nanosheets and graphene nanosheets, and ultrasonically dispersing in the C 3 N 4 Obtaining a dispersion concentrate in the nanosheet dispersion liquidAdding zinc acetate into the dispersion liquid with the concentration of 1-5mg/mL, and completely dissolving to obtain a solution A; respectively weighing sodium carbonate and germanium dioxide, mixing the sodium carbonate and the germanium dioxide according to an equimolar ratio, heating the mixture to 900-1000 ℃ at the speed of 2-5 ℃/min, carrying out heat preservation treatment for 6-12h to obtain a product A, and dissolving the product A in deionized water to prepare a solution B with the concentration of 4-8 mg/mL; slowly adding the solution B into the solution A under the condition of violent stirring, heating to boil, keeping the temperature, stirring and reacting for 2-3 hours, cooling after the reaction is finished, centrifugally separating and precipitating, washing with ethanol and deionized water in sequence, and drying to obtain the product;
wherein the zirconium phosphate nano-sheet, the graphene nano-sheet and the C 3 N 4 The mass ratio of the nano sheets is (1-3): (0.5-1) (0.5-1); the concentration of zinc acetate in the solution A is 0.08-0.1 mol/L; the mixing volume ratio of the solution A to the solution B is 1: 1.
6. the engineering plastic alloy with enhanced lubrication and wear resistance as claimed in claim 5, wherein the zirconium phosphate nanosheets are alpha-zirconium phosphate nanosheets, and the preparation method thereof comprises the following steps:
weighing alpha-zirconium phosphate and dispersing the alpha-zirconium phosphate in deionized water to obtain a solution C; respectively weighing tromethamine, choline and triethanolamine as stripping aids, dissolving in deionized water to obtain a solution D, slowly adding the solution D into the solution C at room temperature under stirring conditions, continuing stirring for reaction for 1-30min after the addition is finished, performing high-speed centrifugal separation and precipitation after ultrasonic dispersion, and drying to obtain the alpha-zirconium phosphate nanosheets;
wherein the dispersion ratio of the alpha-zirconium phosphate is 2-4g/100 mL; the concentration of the tromethamine, the concentration of the choline and the concentration of the triethanolamine in the solution D are respectively 0.01-0.1mol/L, 0.04-0.1mol/L and 0.01-0.05mol/L, and the mixing volume ratio of the solution C to the solution D is 1: 1.
7. the engineering plastic alloy with enhanced lubrication and wear resistance as claimed in claim 5, wherein the preparation method of the zirconium phosphate nano-sheets comprises the following steps:
weighing phenylphosphonic acid and dissolving the phenylphosphonic acid in deionized water to prepare a solution E with the concentration of 0.6-1 mol/L; respectively weighing zirconium oxychloride and hydrofluoric acid, preparing into solutions F with the concentrations of 0.15-0.25mol/L and 1-1.5mol/L respectively, adding the solution E into the solution F with the same volume under the stirring condition, sealing a reaction system, carrying out heat preservation reaction at 70-80 ℃ for 36-48h, carrying out centrifugal separation and precipitation after the reaction is finished, washing, and carrying out vacuum drying to remove the solvent, thus obtaining the zirconium phosphate nanosheet.
8. The engineering plastic alloy with the lubricating and wear-resisting enhancement function as claimed in claim 1, wherein the lubricant is one or more of calcium stearate, ethylene bis-hard amide and pentaerythritol tetrastearate alcohol.
9. The engineering plastic alloy with enhanced lubrication and wear resistance as claimed in claim 1, wherein the stabilizer is an organic tin stabilizer or an organic antimony stabilizer.
10. The method for preparing the engineering plastic alloy with the lubricating and wear-resisting enhancement function according to one of the claims 1 to 9, characterized by comprising the following steps:
(1) preparing the wear-resistant agent;
(2) preparing raw materials according to the proportion, firstly stirring and mixing the raw materials in a high-speed mixer for 1-30min, then putting the dispersed raw materials into an extruder, feeding the raw materials at the rotating speed of 40-50rpm, heating the extruder at the temperature of 200-280 ℃, and carrying out melt blending, extrusion, traction, cooling and grain cutting to obtain the lubricating wear-resistant reinforced engineering plastic alloy.
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| CN115322566A (en) * | 2022-09-16 | 2022-11-11 | 无锡腾达精密模塑有限公司 | PA 66-based composite material for motor bearing retainer and preparation method thereof |
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